CN111100300B - Polymerizable polyether organic silicon, composition, preparation method and application thereof - Google Patents
Polymerizable polyether organic silicon, composition, preparation method and application thereof Download PDFInfo
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- CN111100300B CN111100300B CN201811248735.0A CN201811248735A CN111100300B CN 111100300 B CN111100300 B CN 111100300B CN 201811248735 A CN201811248735 A CN 201811248735A CN 111100300 B CN111100300 B CN 111100300B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08J2323/12—Polypropene
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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Abstract
The invention relates to polymerizable polyether organic silicon for an easy-to-clean coating of a transparent polyolefin agricultural film, a composition, a preparation method and application thereof, and mainly solves the problem that the common easy-to-clean coating or hydrophilic coating cannot be simultaneously coated on the front side and the back side of the polyolefin agricultural film. The invention adopts a polymerizable polyether organic silicon, which has a molecular general formula shown in a formula (I): in the formula (I), m 1 And m 2 Independently selected from integers of 0-30; n is 1 A number selected from 2 to 10; n is 2 A number selected from 0 to 30; y being selected from acyl groups containing unsaturated bondsThe technical scheme better solves the problem and can be used for preparing easy-to-clean coatings on the surfaces of various transparent plastic films.
Description
Technical Field
The invention relates to a polymerizable polyether organic silicon, a composition, a preparation method and application thereof.
Background
The greenhouse film has the advantages of excellent low temperature resistance, light transmission, low price, convenient processing and the like, and is widely applied to industrial and agricultural production. Due to the hydrophobicity of the plastic material, a large amount of water drops are attached to the inner wall of the plastic shed covered by the shed film without coating treatment due to the change of temperature and humidity, and the light transmittance of the shed film is seriously influenced, so that the rise of the temperature in the shed is influenced, and the photosynthesis of plants in the shed is weakened. Meanwhile, the incidence of crops is increased when fog drops on the greenhouse film drop on the crops. Since plastic materials are easy to generate static electricity, dust is easy to adsorb on the surface of the greenhouse film due to the interaction of the static electricity in outdoor application, and the light transmittance of the film is also reduced. In addition, the static electricity generated by the greenhouse film brings trouble to the processing process.
There have been some products that use silane polyether materials with small molecules added to the film to impart antistatic, easy-to-clean properties to the film. However, the small molecular materials migrated to the surface of the film are easily lost, and may stick dust or other impurities in the air, thereby causing disadvantages such as poor antifouling effect.
In order to develop long-acting antistatic and easy-to-clean coatings. The invention develops an easy-to-clean coating composition for greenhouse films. When the easy-cleaning composition master batch is blended and extruded with the base resin of the blown film, molecules of the easy-cleaning composition can spontaneously migrate to the surface of the film. Under the irradiation of ultraviolet light, the polymerizable polyether silane monomer will polymerize to form a polymer. And because the good light transmittance of the greenhouse film and the polymerizable polyether silane composition are diffused on the front side and the back side of the film, easy-to-clean coatings can be formed on the two sides of the greenhouse film simultaneously by using the process, and the problems of difficulty in the process of preparing the coatings on the front side and the back side of the greenhouse film simultaneously in the film blowing process and static elimination are solved. This technology is also expected to be applied to the preparation of easy-to-clean coatings on the surfaces of various transparent plastic articles.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the effect duration time of the antistatic and easy-to-clean coating of the greenhouse film in the prior art is short, and the super-hydrophilic coatings can not be prepared on the front side and the back side of the greenhouse film on a production line simultaneously. The polymerizable polyether silane composition prepared from the organic silicon has obvious reaction activity under ultraviolet irradiation, can directly form a super-hydrophilic coating on the front side and the back side of a greenhouse film at the same time, and better solves the two problems.
The second technical problem to be solved by the present invention is to provide an application of polymerizable polyether organic silicon in greenhouse film corresponding to the first technical problem.
The invention aims to solve the third technical problem of providing the problems that the coating in the prior art is antistatic and easy to clean, has short effect duration and cannot prepare super-hydrophilic coatings on the front side and the back side of the greenhouse film on a production line. The prepared polymerizable polyether silane composition has obvious reaction activity under ultraviolet irradiation, can directly form antistatic and easily-cleaned coatings on the front and back surfaces of a greenhouse film, and better solves the two problems.
The fourth technical problem to be solved by the invention is to provide a preparation method of the polymerizable polyether organic silicon composition corresponding to the third technical problem.
The fifth technical problem to be solved by the present invention is to provide an application method of the polymerizable polyether silicone composition corresponding to the third technical problem.
The sixth technical problem to be solved by the present invention is to provide a film comprising an antistatic, easy-to-clean coating formed from the polymerizable polyether silicone composition described above in the third technical problem.
The seventh technical problem to be solved by the present invention is to provide a multilayer composite greenhouse film, wherein the outermost layer and the innermost layer of the multilayer composite greenhouse film both contain a coating layer formed from the polymerizable polyether silicone composition described above for solving the third technical problem. The outermost layer has a good hydrophobic dustproof effect, and the innermost layer has a good hydrophilic anti-dripping performance.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a polymerizable polyether silicone having a general molecular formula of formula (I):
in the formula (I), m 1 And m 2 Independently selected from integers of 0-30; n is 1 A number selected from 2 to 10; n is a radical of an alkyl radical 2 A number selected from 0 to 30; y is selected from acyl containing unsaturated bonds.
In the above technical solution, the Y is preferably at least one of an acyloxy group or an amido group containing an unsaturated bond; further, Y is preferably at least one selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, or an acyloxy group having another unsaturated bond; or preferably at least one selected from the group consisting of methacrylamido, diallylamino and allylamino groups.
In order to solve the second technical problem, the invention adopts the technical scheme that: the application of the polymerizable polyether organic silicon in the technical scheme for solving the technical problem in greenhouse films.
In the above technical solution, in the application method, preferably, the polymerizable polyether silicone forms an easy-to-clean coating on the surface layer of the greenhouse film, and more preferably, an antistatic easy-to-clean coating is formed on the surface layer of the greenhouse film in the form of the polymerizable polyether silicone composition described below to solve the third technical problem.
In order to solve the third technical problem, the invention adopts the technical scheme that:
a polymerizable polyether silane composition comprising, in parts by weight:
(1) 0.01-80 parts of any polymerizable polyether organic silicon in the technical scheme for solving the technical problem;
(2) 0.01-20 parts of a photoinitiator;
(3) 0.01-5 parts of polymerization inhibitor.
In the technical scheme, the polymerizable polyether organic silicon is more preferably 20-60 parts.
In the technical scheme, the photoinitiator is more preferably 1-10 parts;
in the above technical solution, the polymerizable polyether silicone composition preferably further includes: (4) 0.01-10 parts of a sensitizer, more preferably 1-10 parts; the sensitizer is preferably selected from the group consisting of dimethylamino benzoate, methylaminobenzaldehyde, methyldiethanolamine, diethyl (dibutyl) ethanolamine, triethanolamine, diallylamine or allylamine.
In the technical scheme, the photoinitiator is preferably ITX, 1173, TPO, BAPO, I-907, BMS or benzophenone sulfonium; more preferably at least one of ITX and BAPO.
In the above technical solution, the carrier resin of the polymerizable polyether silane preferably further comprises, in parts by weight: (5) 30-95 parts of carrier resin, and more preferably 40-90 parts of carrier resin; the carrier resin may be polyethylene, polypropylene, polystyrene, linear low density polyethylene, linear high density polyethylene, polyacrylate, polymethacrylate, etc., and more preferably polyethylene, polypropylene, and various transparent plastics.
In the above technical solution, the carrier resin of the polymerizable polyether silane preferably further comprises, in parts by weight: (6) 0-40 parts of hydrophilic comonomer; further, the hydrophilic comonomer is preferably at least one of maleic anhydride, maleic acid and maleic acid mono-polyoxyethylene ether ester.
In order to solve the fourth technical problem, the technical scheme adopted by the invention is as follows: a method of preparing a polymerizable polyether silane composition comprising the steps of:
(1) preparation of polymerizable polyether silicone
Silicone oil and degree of polymerization EO ═ n 2 Reacting the polyether of (a) with a silicone oil in the presence of a catalyst and a solvent; after the reaction is finished, adding a polymerization inhibitor and a monomer containing unsaturated bond acyloxy or amide for reaction, and then carrying out post-treatment to obtain the polymerizable polyether organic silicon;
(2) preparation of polymerizable polyether silicone composition
Uniformly mixing required amounts of polymerizable polyether silicone, photoinitiator, polymerization inhibitor, optional sensitizer, optional carrier resin and optional hydrophilic comonomer, and extruding by using a screw extruder to obtain the polymerizable polyether silicone composition.
In order to solve the fifth technical problem, the invention adopts the technical scheme that: the application of the polymerizable polyether organic silicon composition in any one of the technical schemes for solving the technical problems in the third technical scheme in greenhouse films.
In the above technical scheme, the application is preferably to mix the polymerizable polyether silane composition with a polymer (such as polyolefin) to extrude and blow a film; after forming a film, ultraviolet light is used for irradiation and curing to form a long-acting antistatic coating which is easy to clean.
In order to solve the sixth technical problem, the technical scheme adopted by the invention is as follows: a film comprising a film layer formed from the polymerizable polyether silane composition according to any one of the third technical means for solving the above-mentioned problems.
In the above technical scheme, the polymerizable polyether silane is not sensitive to the carrier resin, and can be polymers such as polyethylene, polypropylene, low density polyethylene, high density polyethylene and the like which are well known to those skilled in the art.
In order to solve the seventh technical problem, the technical scheme adopted by the invention is as follows: a multi-layer composite greenhouse film has at least two film layers; characterized in that the outermost layer contains a film layer formed from the polymerizable polyether silane composition according to any one of the third technical aspects of the above technical problems, wherein the length of the polyether segment in the polymerizable polyether silane is longDegree n 2 0-2 parts of hydrophilic comonomer, 0-0.02 part of hydrophilic comonomer; the innermost film contains a film layer formed by the polymerizable polyether silane composition in any one of the three technical problems, wherein the length n of the polyether chain segment in the polymerizable polyether silane is 2 The hydrophilic comonomer is selected from 15-30 parts, and the addition amount of the hydrophilic comonomer is selected from 20-40 parts.
In the above technical scheme, n is contained 2 The film layer of the outermost film with the value and the content of the hydrophilic comonomer has better dustproof effect; containing said n 2 The film layer of the innermost film with the value and the content of the hydrophilic comonomer has better anti-dripping performance; the multilayer composite shed film has good dustproof effect and good anti-dripping performance.
In the above technical solution, the outermost layer is an outer surface layer of the composite greenhouse film when in use; the innermost layer refers to the inner surface layer of the composite greenhouse film in use.
In the above technical scheme, the composite greenhouse film is preferably formed by compounding 2-12 film layers containing the polymerizable polyether silane composition in any one of the three technical schemes.
The reactivity and hydrophilicity of the polymerizable polyether silane compositions of the present invention are the primary factors affecting the structure and performance of the coating. The polymerizable polyether silane composition can be used for constructing a long-acting easy-cleaning coating on the surfaces of various plastic greenhouse films. The polymerizable polyether silane prepared by the invention has the advantages of good aging resistance, easily obtained raw materials, mature synthetic route, lower final product cost and the like.
By adopting the technical scheme of the invention, the prepared polymerizable polyether silane composition can form a long-acting antistatic easy-to-clean coating on the surface of the greenhouse film, and a long-acting anti-dripping coating can be formed on the inner surface of the greenhouse film, so that a better effect is achieved.
The present invention will be further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
Adding 30 grams of 801 silicone oil, 14.4 grams of allyl glycol ether and 25.15 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 0.9 microliter of 0.1 percent by weight chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, continuing to react for 8 hours, and finishing. Transferring 50 g of the reaction solution into a 250ml four-neck flask, adding 0.0637 g of hydroquinone and 6.38 g of acryloyl chloride, adding 3.45 g of triethanolamine after uniformly stirring, heating to 113 ℃ after uniformly stirring, and reacting for 12 hours to finish the reaction. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. This was washed twice to give a toluene solution of the polymerizable polyether silane. 0.06 g of p-hydroxyanisole is added, and toluene is removed by rotary evaporation at 100 ℃ to obtain the polymerizable polyether silane.
60 g of polymerizable polyether silane, 20 g of 2-isopropyl thioxanthone, 15 g of ethyl 4-dimethylaminobenzoate and 5 g of p-hydroxyanisole are uniformly mixed, then the mixture is mixed with 10kg of polyolefin resin in a high-speed mixer, and the mixture is extruded and granulated by a double-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. Then 1Kg of master batch and 19Kg of polyolefin are mixed and extruded into a blown film, and the polyether silane coating on the surface of the film is cured by irradiating the film for 1 second by using a 365nm LEDUV light source on a production line of the blown film.
[ example 2 ]
Adding 30 grams of 801 silicone oil, 14.4 grams of APEG-1000 polyether and 25.15 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 0.9 microliter of 0.1 wt% chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. Transferring 50 g of the reaction liquid into a 250ml four-neck flask, adding 0.0637 g of p-hydroxyanisole and 9 g of methacryloyl chloride, stirring uniformly, adding 4 g of triethanolamine, stirring uniformly, heating to 113 ℃, reacting for 12 hours, and finishing. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
60 g of target compound, 20 g of 2-isopropylthioxanthone, 15 g of ethyl 4-dimethylaminobenzoate and 5 g of p-hydroxyanisole are uniformly mixed, then mixed with 10kg of polystyrene resin in a high-speed mixer, and extruded and granulated by a double-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. Then 1Kg of master batch and 19Kg of polystyrene are mixed and extruded into a blown film, and the polyether silane coating on the surface of the film is cured by irradiating the film for 1 second by using a 365nm LEDUV light source on a film blowing production line.
[ example 3 ]
Adding 30 grams of 801 silicone oil, 8.54 grams of APEG-2000 polyether and 33.67 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 1.2 microliters of 0.1 wt% of isopropanol solution of chloroplatinic acid, heating to 113 ℃ after stirring uniformly, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. Transferring 50 g of the reaction liquid into a 250ml four-neck flask, adding 0.0637 g of p-hydroxyanisole and 9 g of methacryloyl chloride, stirring uniformly, adding 4 g of triethanolamine, stirring uniformly, heating to 113 ℃, reacting for 12 hours, and finishing. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for layering, and the lower layer brine was separated. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole is added, and toluene is removed by rotary evaporation at 100 ℃ to obtain the target compound.
60 g of target compound, 20 g of 2-isopropyl thioxanthone, 15 g of ethyl 4-dimethylaminobenzoate and 5 g of p-hydroxyanisole are uniformly mixed, then the mixture is mixed with 10kg of polypropylene resin in a high-speed mixer, and the mixture is extruded and granulated by a double-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. Then 1Kg of master batch and 19Kg of polypropylene are mixed and extruded into a blown film, and the polyether silane coating on the surface of the film is cured by irradiating the film for 1 second by using a 365nm LEDUV light source on a production line of the blown film.
[ example 4 ]
Adding 30 grams of 801 silicone oil, 8.54 grams of APEG-2000 polyether and 33.67 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 1.2 microliters of 0.1 wt% chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. Transferring 50 g of the reaction liquid to a 250ml four-neck flask, adding 0.0637 g of p-hydroxyanisole and 7 g of acryloyl chloride, adding 4 g of triethanolamine after uniformly stirring, heating to 113 ℃ after uniformly stirring, and reacting for 12 hours to finish. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
After 60 g of the target compound, 20 g of 2-isopropylthioxanthone, 15 g of ethyl 4-dimethylaminobenzoate and 5 g of p-hydroxyanisole are uniformly mixed, 10kg of polymethacrylate resin is mixed in a high-speed mixer, and the mixture is extruded and granulated by a double-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. Then 1Kg of master batch and 19Kg of polymethacrylate are mixed and extruded into a blown film, and the polyether silane coating on the surface of the film is cured by irradiating the film for 1 second by using a 365nm LEDUV light source on a film blowing production line.
[ example 5 ]
Adding 30 grams of 801 silicone oil, 14.4 grams of APEG-1000 polyether and 25.15 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 0.9 microliter of 0.1 wt% chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. Transferring 50 g of the reaction solution into a 250ml four-neck flask, adding 0.0637 g of hydroquinone and 6.38 g of acryloyl chloride, adding 3.45 g of triethanolamine after uniformly stirring, heating to 113 ℃ after uniformly stirring, and reacting for 12 hours to finish the reaction. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
60 g of the target compound, 15 g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of ethyl 4-dimethylaminobenzoate and 5 g of p-hydroxyanisole are uniformly mixed, then mixed with 10kg of low-density resin in a high-speed mixer, and extruded and granulated by a twin-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. Then 1Kg of master batch and 19Kg of low density mixture are extruded into blown film, and the film is irradiated by a 365nm LEDUV light source on a production line of the blown film for 1 second to cure the polyether silane coating on the surface.
[ example 6 ]
Adding 30 grams of 801 silicone oil, 14.4 grams of APEG-1000 polyether and 25.15 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 0.9 microliter of 0.1 wt% chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. 50 g of the reaction solution was transferred to a 250ml four-necked flask, and 0.0637 g of hydroquinone and 7 g of diallylamine were added thereto, and the mixture was stirred uniformly and reacted at room temperature for 2 hours. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
After 60 g of the target compound, 15 g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of dimethylamino benzoate, 10 g of pentaerythritol tetrakis (3-mercaptopropionate), and 5 g of p-hydroxyanisole were mixed uniformly, the mixture was mixed with 10kg of polymethacrylate resin in a high-speed mixer, and extruded and granulated by a twin-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. 1Kg of master batch and 19Kg of polymethacrylate resin are mixed and extruded to form a blown film, and the film is irradiated by a 365nm LEDUV light source on a blown film production line for 1 second for curing.
[ example 7 ]
30 g of 801 silicone oil, 5.7 g of APEG-2000 polyether and 25.15 g of toluene are added into a 250ml four-neck flask, stirred and heated to 60 ℃, then 1.2 microliter of 0.1 percent of weight chloroplatinic acid isopropanol solution is added, after being stirred uniformly, the temperature is raised to 113 ℃, after 5 hours of reaction, 100ml of toluene is added, and the reaction is continued for 8 hours, and then the reaction is finished. 50 g of the reaction solution was transferred to a 250ml four-necked flask, and 0.0637 g of hydroquinone and 7 g of methylallylamine were added thereto, and the mixture was stirred uniformly and reacted at room temperature for 2 hours. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
After 60 g of the target compound, 15 g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of dimethylamino benzoate, 10 g of pentaerythritol tetrakis (3-mercaptopropionate), and 5 g of p-hydroxyanisole were mixed uniformly, the mixture was mixed with 10kg of methacrylate resin in a high-speed mixer, and extruded and granulated by a twin-screw extruder to obtain 10kg of master batch containing 1 wt% of the polymerizable polyether silane composition. 1Kg of master batch and 19Kg of methacrylate resin were mixed and extruded to form a blown film, and the film was irradiated with a 365nm LEDUV light source for 1 second to cure on a blown film line.
[ example 8 ]
Adding 30 grams of 801 silicone oil, 5.4 grams of APEG-2000 polyether and 25.15 grams of toluene into a 250ml four-neck flask, stirring and heating to 60 ℃, adding 1.2 microliters of 0.1 wt% chloroplatinic acid isopropanol solution, after stirring uniformly, heating to 113 ℃, reacting for 5 hours, adding 100ml of toluene, and continuing to react for 8 hours. 50 g of the reaction solution was transferred to a 250ml four-necked flask, and 0.0637 g of hydroquinone and 7 g of methylallylamine were added thereto, and the mixture was stirred uniformly and reacted at room temperature for 2 hours. The reaction solution was transferred to a 500ml separatory funnel, 80 ml of 15% wtNaCl brine and 40 ml of isopropanol were added, followed by vigorous shaking, standing for delamination, and the lower brine was separated off. The toluene solution of the target product is obtained by washing twice. 0.06 g of p-hydroxyanisole was added, and toluene was removed by rotary evaporation at 100 ℃ to obtain the objective compound.
60 g of the target compound, 15 g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of dimethylamino benzoate, 10 g of triethanolamine tris (3-mercaptopropionate) and 5 g of p-hydroxyanisole were mixed uniformly, then mixed with 10kg of low-density polyethylene resin in a high-speed mixer, and extruded and granulated by a twin-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition. 1Kg of master batch and 19Kg of low density polyethylene resin were mixed and extruded to blow a film, and the film was irradiated with a 365nm LEDUV light source for 1 second to cure on a film blowing line.
[ example 9 ]
60 g of the objective compound synthesized in example 1, 15 g of phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of dimethylaminobenzoate, 10 g of triethanolamine tris (3-mercaptopropionate), and 5 g of p-hydroxyanisole were mixed uniformly, and then mixed with 10kg of a low-density polyethylene resin in a high-speed mixer, and extruded and granulated by a twin-screw extruder to obtain 10kg of a master batch containing 1 wt% of a polymerizable polyether silane composition.
60 g of the target compound synthesized in example 8, 40 g of maleic acid polyoxyethylene ether monoester, 15 g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 10 g of dimethylamino benzoate, 10 g of tris (3-mercaptopropionic acid) triethanolamine ester and 5 g of p-hydroxyanisole were mixed uniformly, and then mixed with 10kg of low-density polyethylene resin at a high speed, and extruded and granulated by a twin-screw extruder to obtain 10kg of master batch containing 1 wt% of polymerizable polyether silane composition.
The three-layer co-extrusion film blowing line is used for manufacturing a three-layer co-extrusion shed film, and the three layers respectively comprise: the first master batch of this example was mixed with the low density polyethylene resin to extrude the outermost layer, the low density polyethylene resin alone was used to extrude the intermediate layer, and the second master batch of this example was mixed with the low density polyethylene resin to extrude the innermost layer. The three-layer co-extrusion film blowing line consists of three single-screw extruders and a three-layer composite neck mold. By controlling the rotation speed of the screw, the internal screw: the method comprises the following steps: the thickness ratio of the outer three layers is 1:2:1, and the total thickness of the film is controlled to be about 120 micrometers. And irradiating the film by using a 365nm LEDUV light source for 1 second after the drawing process is finished, and curing the polymerizable polyether silane composition which migrates to the surface of the composite film.
[ example 10 ]
The contact angles of the surfaces of the films prepared in examples 1 to 8 and comparative example 1 were tested on a Kruss DSA100 type contact angle meter at room temperature. The values of the measured contact angles are shown in Table 1.
TABLE 1 contact Angle testing of agricultural film samples
Sample numbering | Contact angle (°) |
Example 1 | 102 |
Example 2 | <10 |
Example 3 | Spreading out |
Example 4 | Spreading out |
Example 5 | <10 |
Example 6 | <10 |
Example 7 | Spreading out of a film |
Example 8 | Spreading out |
Example 9 | Outer side 102, inner side spread |
Comparative example 1 | 90 |
Comparative example 1
The low density polyethylene was directly extruded into blown film and the film was irradiated with a 365nm led uv light source for 1 second on the blown film line to obtain a comparative sample.
Claims (8)
1. A polymerizable polyether silicone composition comprising, in parts by weight:
(1) 0.01-80 parts of polymerizable polyether organic silicon;
(2) 0.01-20 parts of a photoinitiator;
(3) 0.01-5 parts of a polymerization inhibitor;
(4) 0.01-10 parts of a sensitizer;
(5) 30-95 parts of carrier resin;
(6) 0-40 parts of hydrophilic comonomer;
the polymerizable polyether silicone has a general molecular formula shown in formula (I):
in the formula (I), m 1 And m 2 Independently selected from integers of 0 to 30 and m 1 Is not 0; n is 1 A number selected from 2 to 10; n is 2 Is selected from a number from 0 to 30 and n 2 Is not 0; y is selected from acyl containing unsaturated bonds;
the hydrophilic comonomer is maleic anhydride, maleic acid and maleic acid mono-polyoxyethylene ether ester;
the carrier resin is at least one selected from polyethylene, polypropylene, polystyrene and polyacrylate.
2. The polymerizable polyether silicone composition of claim 1, the carrier resin being selected from at least one of linear low density polyethylene, linear high density polyethylene, polymethacrylate.
3. The polymerizable polyether silicone composition of claim 1, characterized in that the photoinitiator is a thioxanthone photoinitiator, a benzophenone photoinitiator, an acylphosphorous oxide photoinitiator, an alkyl benzophenone photoinitiator, a benzil, benzoin and derivatives, and a cationic photoinitiator; the polymerization inhibitor is selected from p-hydroxyanisole, hydroquinone and phenothiazine.
4. The polymerizable polyether silicone composition of claim 1 wherein the sensitizer is selected from the group consisting of dimethylamino benzoate, methylamine benzaldehyde, methyl diethanolamine, diethyl (dibutyl) ethanolamine, triethanolamine, diallylamine or allylamine.
5. A method for preparing the polymerizable polyether silicone composition according to any one of claims 1 to 4, comprising the following steps:
(1) preparation of polymerizable polyether silicone
Silicone oil with polymerization degree of n 2 Reacting the polyether of (a) with a silicone oil in the presence of a catalyst and a solvent; after the reaction is finished, adding a polymerization inhibitor and an acyloxy or acylamino monomer containing an unsaturated bond for reaction, and then carrying out post-treatment to obtain the polymerizable polyether organic silicon;
(2) preparation of polymerizable polyether silicone composition
Uniformly mixing the required amount of polymerizable polyether organic silicon, photoinitiator, polymerization inhibitor, sensitizer, carrier resin and optional hydrophilic comonomer, and extruding by using a screw extruder to obtain the polymerizable polyether organic silicon composition.
6. Use of a polymerizable polyether silicone composition according to any one of claims 1 to 4 in a film.
7. A film comprising the polymerizable polyether silicone composition according to any one of claims 1 to 4.
8. A multi-layer composite greenhouse film has at least two film layers; characterized in that the outermost layer comprises a film layer formed by the polymerizable polyether organic silicon composition as claimed in any one of claims 1 to 4, wherein the length n of a polyether chain segment in the polymerizable polyether organic silicon 2 Selected from 0 to 2 and n 2 The addition amount of the hydrophilic comonomer is not 0, and is selected from 0-0.02 part; the innermost film comprises a film layer formed by the polymerizable polyether organic silicon composition as claimed in any one of claims 1 to 4, wherein the length n of a polyether chain segment in the polymerizable polyether organic silicon 2 The hydrophilic comonomer is selected from 15-30 parts, and the addition amount of the hydrophilic comonomer is selected from 20-40 parts.
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CN102170940A (en) * | 2008-10-03 | 2011-08-31 | 迈图高新材料公司 | Hydrophilic silicone monomers, process for their preparation and thin films containing the same |
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WO2014121030A2 (en) * | 2013-01-31 | 2014-08-07 | Momentive Performance Materials Inc. | Water soluble silicone material |
CN106550800A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Polyolefin awning film and preparation method thereof |
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CN102170940A (en) * | 2008-10-03 | 2011-08-31 | 迈图高新材料公司 | Hydrophilic silicone monomers, process for their preparation and thin films containing the same |
WO2014121030A2 (en) * | 2013-01-31 | 2014-08-07 | Momentive Performance Materials Inc. | Water soluble silicone material |
CN103736407A (en) * | 2014-01-24 | 2014-04-23 | 哈尔滨工业大学 | Modifying method for hydrophilia of PVDF (Polyvinylidene Fluoride) micro-filtration membrane |
CN106550800A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Polyolefin awning film and preparation method thereof |
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